Plastic material

ABSTRACT

A material comprising the reaction product of an A-side having a prepolymer isocyanate, preferably a prepolymer diisocyanate and a B-side having a cross-linker comprising a multifunctional alcohol, a first vegetable oil, preferably a blown/oxidized vegetable oil, most preferably a blown/oxidized soybean oil, and a catalyst, wherein the first vegetable oil and the cross-linking agent are substantially non-esterfied prior to combining the A-side with the B-side and the method of producing the same.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a division of and claims the benefit of U.S.patent application Ser. No. 10/253,252, filed on Sep. 24, 2002, which isa continuation of U.S. Pat. No. 6,465,569, which is based upon andclaims the benefit of PCT Application No. WO 00/15684, filed on Sep. 17,1999, which is a continuation-in-part and claims the benefit of U.S.patent application Ser. No. 09/154,340, which has now issued as U.S.Pat. No. 6,180,686.

BACKGROUND OF THE INVENTION

[0002] Because of their widely ranging mechanical properties and theirability to be relatively easily machined and formed, plastic foams andelastomers have found wide use in a multitude of industrial and consumerapplications. In particular, urethane foams and elastomers have beenfound to be well suited for many applications. Automobiles, forinstance, contain a number of components, such as cabin interior parts,that are comprised of urethane foams and elastomers. Such urethane foamsare typically categorized as flexible, semi-rigid, or rigid foams withflexible foams generally being softer, less dense, more pliable, andmore subject to structural rebound subsequent to loading than rigidfoams.

[0003] The production of urethane foams and elastomers are well known inthe art. Urethanes are formed when isocyanate (NCO) groups react withhydroxyl (OH) groups. The most common method of urethane production isvia the reaction of a polyol and an isocyanate which forms the backboneurethane group. A cross-linking agent may also be added. Depending onthe desired qualities of the final urethane product, the preciseformulation may be varied. Variables in the formulation include the typeand amounts of each of the reactants.

[0004] In the case of a urethane foam, a blowing agent is added to causegas or vapor to be evolved during the reaction. The blowing agentcreates the void cells in the final foam, and commonly is a solvent witha relatively low boiling point or water. A low boiling solventevaporates as heat is produced during the exothermic isocyanate/polyolreaction to form vapor bubbles. If water is used as a blowing agent, areaction occurs between the water and the isocyanate group to form anamine and carbon dioxide (CO₂) gas in the form of bubbles. In eithercase, as the reaction proceeds and the material solidifies, the vapor orgas bubbles are locked into place to form void cells. Final urethanefoam density and rigidity may be controlled by varying the amount ortype of blowing agent used.

[0005] A cross-linking agent is often used to promote chemicalcross-linking to result in a structured final urethane product. Theparticular type and amount of cross-linking agent used will determinefinal urethane properties such as elongation, tensile strength,tightness of cell structure, tear resistance, and hardness. Generally,the degree of cross-linking that occurs correlates to the flexibility ofthe final foam product. Relatively low molecular weight compounds withgreater than single functionality are found to be useful ascross-linking agents.

[0006] Catalysts may also be added to control reaction times and toeffect final product qualities. The effects of catalysts generallyinclude the speed of the reaction. In this respect, the catalystinterplays with the blowing agent to effect the final product density.The reaction should proceed at a rate such that maximum gas or vaporevolution coincides with the hardening of the reaction mass. Also, theeffect of a catalyst may include a faster curing time so that a urethanefoam may be produced in a matter of minutes instead of hours.

[0007] Polyols used in the production of urethanes are petrochemicals.Polyester polyols and polyether polyols being the most common polyolsused in urethanes production. For rigid foams, polyester or polyetherpolyols with molecular weights greater than 6,000, are generally used.For semi-rigid foams, polyester or polyether polyols with molecularweights of 3,000 to 6,000 are generally used, while for flexible foams,shorter chain polyols with molecular weight of 600 to 4,000 aregenerally used. There is a very wide variety of polyester and polyetherpolyols available for use, with particular polyols being used toengineer and produce a particular urethane elastomer or foam havingdesired particular final toughness, durability, density, flexibility,compression set ratios and modulus, and hardness qualities. Generally,higher molecular weight polyols and lower functionality polyols tend toproduce more flexible foams than do lighter polyols and higherfunctionality polyols. In order to eliminate the need to produce, store,and use different polyols, it would be advantageous to have a singleversatile component that was capable of being used to create finalurethane foams of widely varying qualities.

[0008] Further, use of petrochemicals such as polyester or polyetherpolyols is disadvantageous for a variety of reasons. As petrochemicalsare ultimately derived from petroleum, they are a non-renewableresource. The production of a polyol requires a great deal of energy, asoil must be drilled, extracted from the ground, transported torefineries, refined, and otherwise processed to yield the polyol. Theserequired efforts add to the cost of polyols and to the disadvantageousenvironmental effects of its production. Also, the price of polyolstends to be somewhat unpredictable as it tends to fluctuate based on thefluctuating price of petroleum.

[0009] Also, as the consuming public becomes more aware of environmentalissues, there are distinct marketing disadvantages topetrochemical-based products. Consumer demand for “greener” productscontinues to grow. As a result, it would be most advantageous to replacepolyester or polyether polyols, as used in the production of urethaneelastomers and foams, with a more versatile, renewable, less costly, andmore environmentally friendly component.

[0010] Efforts have been made to accomplish this. Plastics and foamsmade using fatty acid triglycerides derived from vegetables have beendeveloped, including soybeans derivatives. Because soybeans are arenewable, relatively inexpensive, versatile, and environmentallyfriendly, they are desirable as ingredients for plastics manufacture.Soybeans may be processed to yield fatty acid triglyceride rich soy oiland protein rich soy flour.

[0011] Unlike urethanes, many plastics are protein based. For thesetypes of plastics, soy protein based formulations have been developed.U.S. Pat. No. 5,710,190, for instance, discloses the use of soy proteinin the preparation of a thermoplastic foam. Such plastics, however, arenot suitable for use in applications that call for the particularproperties of urethanes. Since urethanes don't utilize proteins in theirformulations, soy proteins are not relevant to the manufacture ofurethanes.

[0012] Epoxidized soy oils, in combination with polyols, have also beenused to formulate plastics and plastic foams, including urethanes. Forexample, U.S. Pat. No. 5,482,980 teaches using an epoxidized soy oil incombination with a polyol to produce a urethane foam. A polyester orpolyether polyol remains in the formulation, however. Also, as theepoxidation processing of the soy oil requires energy, material andtime, use of an unmodified soy oil would be more advantageous.

[0013] Efforts have been made to produce a urethane type cellularplastic from un-modified soy oil. U.S. Pat. Nos. 2,787,601 and 2,833,730disclose a rigid cellular plastic material that may be prepared usingany of several vegetable oils, including soy oil as a prepolymercomponent only. The foam disclosed in these patents is made from amultistep process requiring the initial preparation of a prepolymer.Moreover, in the case of U.S. Pat. No. 2,833,730, relatively lowcross-linker concentrations are urged, resulting in questionable productstability. Further, use of a particular isocyanate, namely toluenediisocyanate, is disclosed, which is disadvantageous due to itsrelatively high toxicity.

[0014] An unresolved need therefore exists in industry for a urethaneelastomer, a urethane foam, and a method of producing such materialsthat are based on a reaction between isocyanates alone or as aprepolymer, in combination with, a vegetable oil or a vegetableoil-polyurea polyol blend, are particularly desirable because they arerelatively inexpensive, versatile, renewable, environmentally friendlymaterial such as vegetable oils as a replacement for polyether orpolyester polyols typically employed.

SUMMARY OF THE INVENTION

[0015] One embodiment of the present invention includes a material thatincludes the reaction product of an A-side including a prepolymerisocyanate, preferably a prepolymer diisocyanate, and a B-side includinga vegetable oil, a cross-linking agent having a multi-functionalalcohol, and a catalyst that is substantially non-esterified.

[0016] Yet another embodiment of the present invention further includesa method for preparing a material including the steps of combining anA-side including a prepolymer isocyanate, preferably a prepolymerdiisocyanate, and a B-side including a vegetable oil, a cross-linkingagent having a multi-functional alcohol, and a catalyst that issubstantially non-esterified.

[0017] These and other features, advantages and objects of the presentinvention will be further understood and appreciated by those skilled inthe art by reference to the following specification and claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0018] The preparation of urethanes is well known in the art. They aregenerally produced by the reaction of petro-chemical polyols, eitherpolyester or polyether, with isocyanates. The flexibility or rigidity ofthe foam is dependent on the molecular weight and functionality of thepolyol and isocyanate used.

[0019] Petrochemical polyol-based polyurethanes can be prepared in a onestep or a two step process. In the one step process, what is known inthe art as an A-side reactant is combined with what is known as a B-sidereactant. The A-side is generally considered to comprise an isocyanateor a mixture of diisocyanate. The diisocyanates typically used arediphenylmethane diisocyanate (MDI) or toluylenediisocyanate (TDI). Theparticular isocyanate chosen will depend on the particular finalqualities desired in the urethane.

[0020] The B-side material is generally a solution of a petroleum-basedpolyester or polyether polyol, cross-linking agent, and blowing agent. Acatalyst is also generally added to the B-side to control reaction speedand effect final product qualities. As discussed infra, the use of apetrochemical such as a polyester or polyether polyol is undesirable fora number of reasons.

[0021] It has been discovered, however, that flexible urethane foams ofa high quality can be prepared by substituting the petroleum-basedpolyol in the B-side preparation with a vegetable oil in the presence ofa multi-functional alcohol cross-linking agent. The molar ratio of thehydroxyl (OH) groups of the cross-linking agent hydroxyl (OH) groups tothe vegetable oil is preferably at least 0.7:1, and most preferablybetween about 0.7 and 1.2:1. The replacement is made on a substantially1:1 weight ratio of vegetable oil for replaced petroleum-based polyol.Alternatively, a blend of petroleum-based polyol and vegetable oil maybe used. The process of producing the urethane does not changesignificantly with the petroleum-based polyol replaced by the vegetableoil with all other components and general methods as are generally knownin the art. The qualities of the final flexible, semi-rigid, or rigidurethane foam produced using the vegetable oil are consistent with thoseproduced using a high grade, expensive polyol.

[0022] Further, using a single vegetable oil, urethane foams of varyingand selectable final qualities, including differing flexibility,density, and hardness, can be made by varying only the primaryreactants. It would be difficult, if not impossible, to create suchvaried final foams using a single petroleum-based polyester or polyetherpolyol with the same variations in the remaining reactants. Instead,different petroleum-based polyols would be required to produce suchvaried results.

[0023] The use of vegetable oil in the urethane forming reaction alsorealizes a significant cost savings. Vegetable oils are abundant,renewable, and easily processed commodities, as opposed to polyols,which petroleum derivatives and which entail significant associatedprocessing costs. As such, they may currently be acquired for a cost ofapproximately half that of average grade petroleum-based polyurea,polyester or polyether polyols, and approximately one quarter the costof high grade petroleum-based polyester or polyether polyols. Also, aspolyols derived from petroleum, they are not renewable and carry acertain environmental cost with them. There is a distinct marketingadvantage to marketing products that are based on environmentallyfriendly, renewable resources such as vegetable oils.

[0024] The A-side isocyanate reactant of the urethane of the inventionis preferably comprised of an isocyanate chosen from a number ofsuitable isocyanates as are generally known in the art. Differentisocyanates may be selected to create different properties in the finalproduct. The A-side reactant of the urethane of the invention comprisesdiisocyanate; 4,4′ diphenylmethane diisocyanate; 2,4-diphenylmethanediisocyanate; and modified diphenylmethane diisocyanate. Preferably, amodified diphenylmethane diisocyanate is used. It should be understoodthat mixtures of different isocyanates may also be used.

[0025] The A-side of the reaction may also be a prepolymer isocyanate.The prepolymer isocyanate is typically the reaction product of anisocyanate, preferably a diisocyanate, and most preferably some form ofdiphenylmethane diisocyanate and a vegetable oil. The vegetable oil canbe soy oil, rapeseed oil, cottonseed oil, or palm oil, or any other oilhaving a suitable number of reactive hydroxyl (OH) groups. The mostpreferred vegetable oil is soy oil. To create the prepolymerdiisocyanate, the vegetable oil and isocyanate are mixed in a 1:1 ratiofor 10-15 seconds every 10-15 minutes for a total of 4 hours or untilthe reaction has ended. There will still be unreacted isocyanate (NCO)groups in the prepolymer. However, the total amount of active A-sidematerial has increased through this process. The prepolymer reactionreduces the cost of the A-side component by decreasing the amount ofisocyanate required and utilizes a greater amount of inexpensive,environmentally friendly soy oil. In order to permit the prepolymerdiisocyanate A-side to react with the B-side, additional isocyanate mustbe added to elevate the isocyanate (NCO) level to an acceptable level.

[0026] The B-side reactant of the urethane reaction includes at leastvegetable oil and a cross-linking agent. Typically, a blowing agent anda catalyst are also included in the B-side. It is believed that theisocyanate reacts with the fatty acids of the vegetable oil to producethe polymeric backbone of the urethane.

[0027] The vegetable oils that are suitable for use tend to be thosethat are relatively high in triglyceride concentration and that areavailable at a relatively low cost. The preferred vegetable oil is soyoil, although it is contemplated that other vegetable oils, such asrapeseed oil (also known as canola oil), cottonseed oil, and palm oilcan be used in accordance with the present invention. Except for thepreliminary blowing step where air is passed through the oil to removeimpurities and to thicken it, the soy oil is otherwise unmodified. Itdoes not require esterification as is required for some urethaneproducts of the prior art. The preferred blown soy oil has the followingcomposition: 100% Pure Soybean Oil Air Oxidized Moisture 1.15% FreeFatty Acid 5.92% as OLEIC Phosphorous 55.5 ppm Peroxide Value 137.22Meq/Kg Iron  6.5 ppm Hydroxyl Number 212 mgKOH/g Acid Value 12.46mgKOH/g Sulfur  200 ppm Tin  <.5 ppm

[0028] Except for the use of the preferred unmodified, blown soy oilreplacing the polyol, the preferred B-side reactants used to produce thefoam of the invention are generally known in the art. Accordingly,preferred blowing agents for the invention are those that are likewiseknown in the art and may be chosen from the group comprising 134A HCFC,a hydrochloroflurocarbon refrigerant available from Dow Chemical Co.,Midland Mich.; methyl isobutyl ketone (MIBK); acetone; ahydroflurocarbon; and methylene chloride. These preferred blowing agentscreate vapor bubbles in the reacting mass. Should other blowing agentsbe used that react chemically, such as water reacting with theisocyanate (NCO) groups, to produce a gaseous product, concentrations ofother reactants may be adjusted to accommodate the reaction.

[0029] The cross-linking agents of the foam of the present invention arealso those that are well known in the art. They must be at leastdi-functional (a diol). The preferred cross-linking agents for the foamof the invention are ethylene glycol and 1,4 butanediol; however, otherdiols may be used. It has been found that a mixture of ethylene glycoland 1,4 butanediol is particularly advantageous in the practice of thepresent invention. Ethylene glycol tends to offer a shorter chainmolecular structure with many “dead end” sites, tending to create afirmer final foam resistant to tearing or “unzipping,” while 1,4butanediol offers a longer chain molecular structure, tending to createa softer foam. Proper mixture of the two can create engineered foams ofalmost any desired structural characteristics.

[0030] In addition to the B-side's soy oil and blowing agent, one ormore catalyst may be present. The preferred catalysts for the urethanesof the present invention are those that are generally known in the artand are most preferably tertiary amines chosen from the group comprisingDABCO 33-LV® comprised of 33% 1,4 diaza-bicyclco-octane(triethylenediamine) and 67% dipropylene glycol, a gel catalystavailable from the Air Products Corporation; DABCO® BL-22 blowingcatalyst available from the Air Products Corporation; and POLYCAT® 41trimerization catalyst available from the Air Products Corporation.

[0031] Also as known in the art, the B-side reactant may furthercomprise a silicone surfactant which functions to influence liquidsurface tension and thereby influence the size of the bubbles formed andultimately the size of the hardened void cells in the final foamproduct. This can effect foam density and foam rebound (index ofelasticity of foam). Also, the surfactant may function as a cell openingagent to cause larger cells to be formed in the foam. This results inuniform foam density, increased rebound, and a softer foam.

[0032] A molecular sieve may further be present to absorb excess waterfrom the reaction mixture. The preferred molecular sieve of the presentinvention is available under the trade name L-paste™.

[0033] The flexible and semi-rigid foams of the invention will havegreater than approximately 60% open cells. The preferred flexible foamof the invention will also have a density of from 1 lb. to 45 lb. percubic foot and a hardness of durometer between 20 and 70 Shore “A.”

[0034] The urethane foam of the present invention is produced bycombining the A-side reactant with the B-side reactant in the samemanner as is generally known in the art. Advantageously, use of thevegetable oil to replace the petroleum-based polyol does not requiresignificant changes in the method of performing the reaction procedure.Upon combination of the A and B side reactants, an exothermic reactionensues that may reach completion in anywhere from several minutes toseveral hours depending on the particular reactants and concentrationsused. Typically, the reaction is carried out in a mold so that the foamexpands to fill the mold, thereby creating a final foam product in theshape of the mold.

[0035] The components may be combined in differing amounts to yielddiffering results, as will be shown in the Examples presented in thedetailed description below. Generally, however, the preferred flexiblefoam of the invention B-side mixture, when using the preferredcomponents, is prepared with the following general weight ratios: Blownsoy oil 100 parts Cross-linking agent 8-15 parts Blowing agent 8-15parts Catalyst 1-12 parts

[0036] A petroleum based polyol such as polyether polyol, polyesterpolyol, or polyurea polyol may be substituted for some of the blown soyoil in the B-side of the reaction, however, this is not necessary. Thispreferred B-side formulation is then combined with the A-side to producea foam. The preferred A-side, as discussed previously, is comprised ofMDI or a prepolymer comprised of MDI and a vegetable oil, preferably soyoil. The A-side and B-side are typically, and preferably in anapproximate ratio of about 35 parts to about 85 parts A-side to 100parts B-side.

[0037] Flexible urethane foams may be produced with differing finalqualities using the same vegetable oil by varying the particular otherreactants chosen. For instance, it is expected that the use ofrelatively high molecular weight and high functionality isocyanates willresult in a less flexible foam than will use of a lower molecular weightand lower functionality isocyanate when used with the same vegetableoil. Similarly, it is expected that lower molecular weight and lowerfunctionality cross-linkers will result in a more flexible foam thanwill higher molecular weight and higher functionality cross-linkers whenused with the same vegetable oil. Also, a ethylene glycol cross-linkerwill result in shorter final chains and a firmer foam, while use of abutanediol cross-linker results in longer chains and a softer foam.Moreover, it has been contemplated that chain extenders may also beemployed in the present invention. Butanediol, in addition to acting asa cross-linker, may act as a chain extender.

[0038] Urethane elastomers can be produced in much the same manner asurethane foams, except that a blowing agent is not present to createvoid cells in the material. It has been discovered that useful urethaneelastomers may be prepared using a vegetable oil to replace apetroleum-based polyester or polyether polyol. The preferred elastomerof the invention is produced using diphenylmethane diisocyanate (MDI);1,4 butanediol cross-linking agent; and a vegetable oil, preferably soyoil. A catalyst may be added to the reaction composition to deceleratethe speed of the reaction. The preferred elastomer of the invention isprepared by combining the reactants. An exothermic reaction occurs thatcreates the elastomer. The preferred elastomer has an approximatedensity of 65 lb. to 75 lb. per cubic foot.

[0039] The following examples of preparation of foams and elastomers ofthe invention summarized in Table A will illustrate various embodimentsof the invention. In the Examples, the B-Side (soy oil and othercomponents), once blended, has a shelf life of several months. TheA-side material in the following examples is comprised of modifieddiphenylmethane diisocyanate (MDI). The prepolymer A-side material inthe following examples is the reaction product of a vegetable oil,preferably soy oil, and a modified diphenylmethane diisocyanate (MDI).There are four different MDI materials specified in the followingexamples; all are modified monomeric or polymeric diphenylmethanediisocyanates available from the Bayer Corp., Polymers Division,Rosemont Ill.: “Mondur® MA-2901” (Bayer Product Code No. C-1464);“Mondur®-448” (Bayer Product Code No. G-448), “Mondur® MRS-20”, and“Mondur®-PF”.

[0040] Also, “cure” in the following examples refers to the final, curedfoam taken from the mold. The soy oil used in the following examples isblown soy oil obtained from Cargill, in Chicago, Ill. Catalysts usedinclude “DABCO 33-LV®,” comprised of 33% 1,4-diaza-bicyclo-octane and67% dipropylene glycol available from the Air Products UrethanesDivision; “DABCO® BL-22,” a tertiary amine blowing catalyst alsoavailable from the Air Products Urethanes Division; and “POLYCAT® 41”(n, n′, n″, dimethylamino-propyl-hexahydrotriazine tertiary amine) alsoavailable from the Air Products Urethanes Division.

[0041] Catalysts in the following Examples may be referred to as “frontend,” “back end,” and “blowing”. Front end catalysts tend to speed theearly portion of the reaction, while back end catalysts tend to speedthe later, curing portion of the reaction. A blowing catalyst effectsthe timing of the activation of the blowing agent. Some of the Examplesinclude “L-paste™,” which is a trade name for a molecular sieve forabsorbing water. Some also contain “DABCO® DC-5160,” a siliconesurfactant available from Air Products Urethane Division.

EXAMPLES Example 1

[0042] The B-side material was prepared as follows: 50 g Soy Oil 5 gEthylene Glycol (cross-linker) 1 g Front end catalyst (DABCO 33-LV ®;33% triethylenediamine and 67% dipropylene glycol) 1 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst) 4 g Methyl Isobutyl Ketone(blowing agent)

[0043] Blown soy oil has a molecular weight of about 278, while theethylene glycol has a molecular weight of about 62. Thus, the molarratio of ethylene glycol to blown soy oil is 0.22:1. Since the ethyleneglycol has two hydroxyl (OH) groups with which to cross-link theconstituent fatty acids of the blown soy oil, the molar ratio of thehydroxyl (OH) groups of the ethylene glycol to soy oil is about 0.45:1.The resulting B-side was then combined with an A-side material in aratio of 50 parts A-side to 100 parts B-side. The A-side material iscomprised of Mondur® 448, a modified monomeric diphenylmethanediisocyanate (pMDI). The cure was acceptable; however, the cellularmaterial remained tacky at the surface for 20 minutes.

Example 2

[0044] The B-side is the same as that of Example 1. The A-side iscomprised of MA-2901, a modified diphenylmethane diisocyanate. TheB-side was combined with the A-side in a ratio of 52 parts A-side to 100parts B-side. The cure was acceptable, although the cellular materialremained tacky for 12 minutes.

Example 3

[0045] The A-side was the same as Example 2. The B-side was again thesame as that of Example 1, except that 1.5 parts of methanol were addedas additional blowing agent. The ratio was 52 parts A-side to 100 partsB-side. The sample cured in 1 hour. It was not a favorable result inthat the cellular material foamed and then fell back to solid and roseagain. The methanol apparently had an adverse affect.

Example 4

[0046] B-side: 100 g Soy Oil 5 g Ethylene Glycol (cross-linker) 2.5 gFront end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst) 4 g Methyl Isobutyl Ketone (MIBK)

[0047] The A-side was the same as Example 2. The materials were reactedin a ratio of 50 parts A-side to 100 parts B-side. The results were agood foam, but weak in tensile strength.

Example 5

[0048] The B-side and A-side are the same as in Example 4. However, thematerials were reacted in a ratio of 52 parts A-side to 100 partsB-side. The results were essentially the same as in Example 4 with alittle better tensile strength.

Example 6

[0049] B-Side: 103 g Soy Oil 10 g Ethylene Glycol (cross-linker) 11 gAcetone (Blowing agent) 2.5 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst)

[0050] The molar ratio of ethylene glycol to blown soy oil is 0.44:1.With two hydroxyl (OH) groups with which to cross-link the constituentfatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH)groups of the ethylene glycol to soy oil is about 0.90:1. The A-sidecomprises 52 parts MA-2901, a modified monomeric diphenylmethanediisocyanate, to 100 parts B-side. The resulting foam was hard and itscell size large. It fell back to a solid, largely due to too muchblowing agent.

Example 7

[0051] B-side: 100 g Soy Oil 8 g Ethylene Glycol (cross-linker) 5 gAcetone (Blowing agent) 2.5 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst)

[0052] The molar ratio of ethylene glycol to blown soy oil is 0.35 to 1.With two hydroxyl (OH) groups with which to cross-link the constituentfatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH)groups of the ethylene glycol to soy oil is about 0.70:1. The A-sidecomprises MA-2901, a modified monomeric diphenylmethane diisocyanate,and is present in 51 parts A-side to 100 parts B-side. The resultingfoam is generally a good foam, having low tensile strength but a betterdensity range.

Example 8

[0053] The B-side is the same as that of Example 7. The A-side alsocomprises MA-2901, a modified monomeric diphenylmethane diisocyanate, asin Example 7. The A-side is present in a ratio of 45 parts A-side to 100parts B-side.

Example 9

[0054] The A-side and B-side are the same as in Example 7. However, 72parts A-side were reacted with 100 parts B-side. The resulting foam fellback and did not cure after 1 hour, indicating an overcharge of A-side.

Example 10

[0055] B-side 100 g Soy Oil 11 g Ethylene Glycol (cross-linker) 4 gMethyl Isobutyl Ketone (MIBK) 3 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 3 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst)

[0056] The molar ratio of ethylene glycol to blown soy oil is 0.49:1.With two hydroxyl (OH) groups with which to cross-link the constituentfatty acids of the blown soy oil, the molar ratio of the hydroxyl (OH)groups of the ethylene glycol to soy oil is about 0.99:1. The A-sidecomprised MA-2901, a modified monomeric diphenylmethane diisocyanate.The A-side was reacted with the B-side in a ratio of 50 parts A-side to100 parts B-side. The resulting foam had a 15-minute cure and a veryslow recovery. However, the final cure was insufficient because it didnot occur for 72 hours.

Example 11

[0057] B-side 100 g Soy Oil 11 g Ethylene Glycol (cross-linker) 4 gMethyl Isobutyl Ketone (MIBK) 3 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 3 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst)

[0058] The B-side is as in Example 10. The A-side comprises Mondur® 448,a modified monomeric diphenylmethane diisocyanate, in a ratio of 50parts A-side to 100 parts B-side. The resulting foam cures in 15minutes, but is very crumbly.

Example 12

[0059] B-side 100 g Soy Oil 11 g Ethylene Glycol (cross-linker) 4 gMethyl Isobutyl Ketone (MIBK) 3 g front end catalyst (DABCO 33-LV ®; 33%diaza-bicyclo-octane and 67% dipropylene glycol) 3 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst)

[0060] The B-side is as in Example 10. The A-side comprised 76 partsMA-2901, a modified monomeric diphenylmethane diisocyanate, to 100 partsB-side. The resulting foam cures in 30 minutes, but has a very fast,complete fall back.

Example 13

[0061] B-side 100 g Soy Oil 5 g Ethylene Glycol (cross-linker) 5 g 1,4butanediol (cross-linker) 4 g Methyl Isobutyl Ketone (MIBK) 2.5 g Frontend catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst)

[0062] Ethylene glycol has a molecular weight of about 62 and 1,4butanediol has a molecular weight of about 90. Thus, the molar ratio ofthe ethylene glycol to blown soy oil is 0.22:1 and the molar ratio ofthe 1,4 butanediol to blown soy oil is 0.15:1. Since each of theethylene glycol and 1,4 butanediol have two hydroxyl (OH) groups withwhich to cross-link the constituent fatty acids of the blown soy oil,the molar ratio of the hydroxyl (OH) groups of the 50/50 ethyleneglycol/1,4 butanediol cross-linker mixture to the blown soy oil is about0.75:1. The A-side was reacted at 74 parts MA-2901, a modified monomericdiphenylmethane diisocyanate to 100 parts B-side. The resulting foamcured to the touch within 3 minutes and fully cured within 15 minutes.It has good properties.

Example 14

[0063] B-side 100 g Soy Oil 5 g Ethylene Glycol (cross-linker) 5 g 1,4butanediol (cross-linker) 4 g Methyl Isobutyl Ketone (MIBK) 2.5 g Frontend catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2.5 g Back end catalyst (POLYCAT ^(®) 41;n,n′,n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 2 g Blowcatalyst (DABCO ® BL-22; a tertiary amine catalyst)

[0064] The A-side was reacted at 74 parts, a modified MDI, MA-2901, to100 parts B-side. The resulting foam cured to the touch within 3 minutesand exhibited slightly better initial strength than the foam of Example13. It fully cured within 15 minutes with good properties.

Example 15

[0065] B-side 200 g Soy Oil 7 g Ethylene Glycol (cross-linker) 16 g 1,4butanediol (cross linker) 2.5 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst(DABCO ® BL-22′ a tertiary amine catalyst) 2 g Back end catalyst(POLYCAT ® 41; n,n′,n″,dimethylamino-propyl- hexahydrotriazine tertiaryamine)

[0066] The molar ratio of the ethylene glycol to blown soy oil is 0.15:1and the molar ratio of the 1,4 butanediol to blown soy oil is 0.24:1.Since each of the ethylene glycol and 1,4 butanediol have two hydroxyl(OH) groups with which to cross-link the constituent fatty acids of theblown soy oil, the molar ratio of the hydroxyl (OH) groups of the 50/50ethylene glycol/1,4 butanediol cross-linker mixture to blown soy oil isabout 0.80:1.

[0067] The A-side was reacted at 74 parts, a modified MDI, MA-2901 to100 parts B-side. The resulting foam had very good qualities. The foamexhibited good elastomeric and fast cure (tack-free after 90 seconds)properties and was soft with good elastomeric properties after 1 hour.

Example 16

[0068] The B-side is the same blend as Example 15. The A-side comprises,a modified MDI, Mondur® 448. The A-side was reacted at 74 parts A-sideto 100 parts B-side. The reaction time was good and the resulting foamwas a stiff flexible foam with good elastomeric properties. The foamcontinued to exhibit good elastomeric properties after 1 hour.

Example 17

[0069] B-side 100 g Soy Oil 5 g Ethylene Glycol (cross-linker) 5 g 1,4butanediol (cross-linker) 2.5 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst) 2 g Back end catalyst(POLYCAT ® 41; n,n′,n″,dimethylamino-propyl- hexahydrotriazine tertiaryamine) 2 g Molecular sieve (L-paste ™)

[0070] The molar ratio of the hydroxyl (OH) groups of the 50/50 ethyleneglycol/1,4 butanediol cross-linker mixture to soy oil is again about0.75:1.

[0071] The A-side comprises a 50/50 blend of, a modified MDI, MA-2901and a modified pMDI, Mondur® 448. The A-side was reacted with the B-sideat 74 parts A-side to 100 parts B-side. The resulting foam is a goodfoam with good flexibility, high density, but still needs tensileimprovements.

Example 18

[0072] B-side 200 g Soy Oil 5 g Ethylene Glycol (cross-linker) 21 g 1,4butanediol (cross-linker) 5 g Front end catalyst (DABCO 33-LV ®; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 5 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst) 2 g Back end catalyst(POLYCAT ® 41; n,n′,n″,dimethylamino-propyl- hexahydrotriazine tertiaryamine) 6 g Molecular sieve (L-paste ™)

[0073] The molar ratio of the hydroxyl (OH) groups of the 5/21 ethyleneglycol/1,4 butanediol mixture to blown soy oil is about 0.85:1.

[0074] The A-side comprises a 50/50 blend of a modified MDI, MA-2901 anda modified pMDI, Mondur® 448. The A-side was reacted with the B-side at74 parts A-side to 100 parts B-side. The resulting foam is very similarto that of Example 17 and is a good foam with good flexibility, highdensity, but still needs tensile improvements.

Example 19

[0075] B-side 200 g Soy Oil 22 g Ethylene Glycol (cross-linker) 4 g 1,4butanediol (cross-linker) 2.5 g Front end catalyst (DABCO 33-LV ® ; 33%1,4-diaza-bicyclo-octane and 67% dipropylene glycol) 2.5 g Blow catalyst(DABCO ® BL-22; a tertiary amine catalyst) 5 g Back end catalyst(POLYCAT 41 ®; n,n′,n″,dimethylamino-propyl- hexahydrotriazine tertiaryamine) 16 g Molecular sieve (L-paste ™) 4 g Silicone surfactants(DABCO ® DC-5160)

[0076] The molar ratio of the hydroxyl (OH) groups of the 22/4 ethyleneglycol/1,4 butanediol mixture to blown soy oil is about 1.10:1. TheA-side comprises a modified MDI, MA-290. The A-side and the B-side werereacted at 74 parts A-side to 100 parts B-side. The resulting foamdemonstrated very good properties. It is almost a solid elastomer withgood rebound.

Example 20

[0077] B-side 200 g Soy Oil 22 g Ethylene Glycol (cross-linker) 4 g 1,4butanediol (cross-linker) 10 g Methylene Chloride (blowing agent) 2.5 gFront end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst) 5 g Back end catalyst (POLYCAT ® 41;n,n′,n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 16 gMolecular sieve (L-paste ™) 4 g Silicone surfactants (DABCO ® DC-5160)

[0078] The molar ratio of the hydroxyl (OH) groups of the 22/4 ethyleneglycol/1,4 butanediol mixture to blown soy oil is again about 1.10:1.The A-side comprises a modified MDI, MA-2901, and was reacted at 74parts A-side to 100 parts B-side. The resulting foam was a very goodfoam having uniform cell size, good flex, moderate density, good reboundand higher tensile strength.

Example 21

[0079] B-side 200 g Soy Oil 22 g Ethylene Glycol (cross-linker) 4 g 1,4butanediol (cross-linker) 10 g Methylene Chloride (blowing agent) 2.5 gFront end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst) 5 g Back end catalyst (POLYCAT 41 ®;n,n′,n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 16 gMolecular sieve (L-paste ™) 4 g Silicone surfactants (DABCO ® DC-5160) 2g Green pigment

[0080] The molar ratio of the hydroxyl (OH) groups of the 22/4 ethyleneglycol/1,4 butanediol mixture to blown soy oil is again about 1.10:1.The A-side comprises a modified MDI, MA-2901, and was reacted at 81parts A-side to 100 parts B-side.

Example 22

[0081] B-side 200 g Soy Oil 22 g Ethylene Glycol (cross-linker) 4 g 1,4butanediol (cross-linker) 12 g Methylene Chloride (blowing agent 2.5 gFront end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2.5 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst) 5 g Back end catalyst (POLYCAT 41 ®;n,n′,n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 16 gMolecular sieve (L-paste ™) 4 g Silicone surfactants (DABCO ® DC-5160) 2g Green pigment

[0082] The molar ratio of the hydroxyl (OH) groups of the 22/4 ethyleneglycol/1,4 butanediol mixture to blown soy oil is again about 1.10:1.The A-side comprises a modified MDI, MA-2901. The A-side and the B-sidewere reacted at 80 parts A-side to 100 parts B-side. The resulting foamwas a good foam. It was a stiffer flexible foam with good cell size,good uniformity, and low to moderate density.

Example 23

[0083] B-side 400 g Soy Oil 35 g Ethylene Glycol (cross-linker) 15 g 1,4butanediol (cross-linker) 24 g Methylene Chloride (blowing agent) 5 gFront end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 5 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst) 9 g Back end catalyst (POLYCAT ® 41;n,n′,n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 32 gMolecular sieve (L-paste ™) 12.5 g Silicone surfactants (DABCO ®DC-5160) 4 g Green pigment

[0084] The molar ratio of the hydroxyl (OH) groups of the 35/15 ethyleneglycol/1,4 butanediol mixture to blown soy oil is about 1.00:1. TheA-side comprises a modified MDI, MA-2901, and was reacted at 74 partsA-side to 100 parts B-side. The resulting foam is low in density withpoor tensile strength.

Example 24

[0085] B-side 235 g Soy Oil 25 g Ethylene Glycol (cross-linker) 6 g 1,4butanediol (cross-linker) 12 g Methylene Chloride (blowing agent) 2 gFront end catalyst (DABCO 33-LV ®; 33% 1,4-diaza-bicyclo-octane and 67%dipropylene glycol) 2 g Blow catalyst (DABCO ® BL-22; a tertiary aminecatalyst) 1.75 g Back end catalyst (POLYCAT 41 ®;n,n′,n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 25 gMolecular sieve (L-paste ™)

[0086] The molar ratio of the hydroxyl (OH) groups of the 25/6 ethyleneglycol/1,4 butanediol mixture to soy oil is about 1.50:1. The A-sidecomprises a 2,4′ rich polymeric MDI, Mondur® MRS-20, and was reacted at70 parts to 100 parts B-side. The resulting reaction had no foaming andno real reaction.

Example 25

[0087] Example 24 is repeated with A-side comprising Mondur®-PF, amodified MDI. Again, no foaming and not a good reaction.

Example 26

[0088] Example 24 is again repeated, with the A-side this timecomprising a 50/50 mixture of a modified MDI, MA-2901, and a modifiedpMDI, Mondur® 448. It is reacted at 70 parts to 100 parts B-side.

Example 27

[0089] The A-side comprises a modified MDI, MA-2901. The B-sidecomprises the following: B-side 100 g Soy Oil 7 g Dipropylene-glycol(cross-linker) 2 g Front end catalyst (DABCO 33-LV ®; 33%triethylenediamine and 67% dipropylene glycol) 2 g Back end catalyst(DABCO ® 8154; an amine salt)

[0090] The A-side and B-side reactions were mixed in a ratio of 60 partsA-side to 100 parts B-side. The resultant foam exhibited excellentproperties.

Example 28

[0091] B-side 100 g Soy Oil 3 g Dipropylene glycol (cross-linker) 2 gSurfactant 2 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamineand 67% dipropylene glycol) 2 g Back end catalyst (DABCO ® 8154; anamine salt)

[0092] The A-side and B-side reactions were mixed in a ratio of 60 partsA-side to 100 parts B-side. The resultant reaction produced a foamexhibiting excellent properties.

Example 29

[0093] The A-side and B-side components are identical to those inExample 28. The A-side was reacted with the B-side in a ratio of 68parts A-side and 100 parts B-side. Once again, the foam produced by thereaction had excellent properties.

Example 30

[0094] The A-side comprises a mix of a modified MDI, MA-2901,and amodified pMDI, Mondur® 448. The B-side comprises the following: B-side100 g Soy Oil 3 g Tripropylene glycol (cross-linker) 3 g Dipropyleneglycol (cross-linker) 2 g Front end catalyst (DABCO 33-LV ®; 33%triethylenediamine and 67% dipropylene glycol) 2 g Back end catalyst(DABCO ® 8154; an amine salt)

[0095] The A-side and B-side were mixed in a ratio of 60 parts A-side to100 parts B-side. The resultant foam was a rigid foam exhibitingexcellent properties.

Example 31

[0096] In this example, the A-side was identical to the A-side ofExample 30 and the B-side is identical to Example 30 except for the factthat 6% butanediol was added to the B-side. The A-side and B-side weremixed in a ratio of 60 parts A-side to 100 parts B-side. The resultantfoam was a rigid foam exhibiting excellent properties. The addition ofthe butanediol increased the speed of the reaction compared to Example30.

Example 32

[0097] The A-side comprises polymeric MDI. The B-side comprises thefollowing: B-side 200 g Soy Oil 30 g Ethylene glycol (cross-linker) 15 gButanediol (cross-linker) 5 g Aliphatic amine tetrol (CL-485;cross-linker) 25 g Molecular sieve (L-paste ™) 8 g Front end catalyst(DABCO 33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 5 gBack end catalyst (DABCO ® 1854; an amine salt)

[0098] The A-side and B-side were mixed in a 1:1 ratio. The foamresulting from the chemical reaction was a rigid foam with goodproperties.

Example 33

[0099] B-side 100 g Soy Oil 10 g Butanediol (cross-linker) 6.4 gEthylene glycol (cross-linker) 3 g Aliphatic amine tetrol (cross-linker)3.2 g Front end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67%dipropylene glycol) 3.0 g Back end catalyst (DABCO ® 1854; an aminesalt) 5% Molecular sieve (L-paste ™)

[0100] The A-side and B-side were mixed in a ratio of 35 parts A-side to100 parts B-side. The resulting foam was very good after about 15minutes.

Example 34

[0101] The A-side comprises either MDI or pMDI. The B-side comprised thefollowing: B-side 200 g Soy Oil 200 g Polyurea polyol 48 g Aliphaticamine tetrol (cross-linker) 30 g Ethylene glycol (cross-linker) 3 gFront end catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67%dipropylene glycol) 3 g Back end catalyst (Polycat 41 ®; n, n′, n″,dimethylamino-propyl- hexahydrotriazine tertiary amine) 3 g Tertiaryamine catalyst (DABCO ® BL-22) 7 g Molecular sieve (L-paste ™)

[0102] The A-side and B-side were combined in a ratio of 50 parts A-sideto 100 parts B-side. The result reaction occurred very fast and theresultant elastomer exhibited good properties. Combining the A-side andthe B-side in a ratio of 68 parts A-side to 100 parts B-side alsoresults in an elastomer with good properties.

Example 35

[0103] B-side 300 g Soy Oil 300 g Polyurea polyol (petroleum basedpolyol) 33 g Butanediol (cross-linker) 11.3 g Front end catalyst (DABCO33-LV ®; 33% triethylenediamine and 67% dipropylene glycol) 7.6 g Backend catalyst (Polycat ® 41; n, n′, n″, dimethylamino-propyl-hexahydrotriazine tertiary amine 5 g Aliphatic amine tetrol (DABCO ®CL-485; cross-linker)

[0104] The A-side was blended with the B-side in a ratio of 40 partsA-side to 100 parts B-side. The resultant foam had good properties, butwas slightly hard.

Example 36

[0105] The A-side and B-side are identical to Example 35, however, 5%methylene chloride and 1% of a stabilizing anti-oxidant, Stabaxol® wereadded to the B-side. The A-side and the B-side were mixed in a ratio of32 parts A-side to 100 parts B-side and a ratio of 36.5 parts A-side to100 parts B-side. Both resulting foams were good, soft foams. Theaddition of the methylene chloride as a blowing agent greatly assistedthe reaction without pulling out water thereby allowing the foam to staysoft.

Example 37

[0106] The A-side comprises a 50/50 mixture of modified MDI and modifiedpMDI. The B-side comprises the following: B-side 400 g Soy Oil 400 gPolyurea polyol (petroleum based polyol) 96 g Aliphatic amine tetrol(cross-linker; amine salt) 60 g Ethylene glycol (cross-linker) 6 g Frontend catalyst (DABCO 33-LV ®; 33% triethylenediamine and 67% dipropyleneglycol) 3 g Back end catalyst (tertiary amine catalyst) 6 g Blowcatalyst (DABCO ® BL-22)

[0107] The A-side was combined with the B-side in a ratio of 50 partsA-side to 100 parts B-side. The resultant foam exhibited good overallproperties.

Example 38

[0108] The A-side comprises a polymeric MDI, Mondur® MR light. TheB-side comprises the following: B-side 50 g Soy Oil 50 g Sucrose polyol(Bayer 4035) 10 g Ethylene glycol (cross-linker) 2.5 g Dipropyleneglycol (cross-linker) 3.0 g Front end catalyst 2.0 g Back end catalyst(tertiary block amine catalyst)

[0109] The A-side was mixed with the B-side at the following ratios:A-side B-side  50 100  70 100  80 100  90 100 100 100

[0110] Each mix ratio resulted in a very fast reacting high-density foamexhibiting good qualities overall.

[0111] The above description is considered that of the preferredembodiments only. Modifications of the invention will occur to thoseskilled in the art and to those who make or use the invention.Therefore, it is understood that the embodiments shown in the drawingsand described above are merely for illustrative purposes and notintended to limit the scope of the invention, which is defined by thefollowing claims as interpreted according to the principles of patentlaw, including the doctrine of equivalents.

What is claimed is:
 1. The material comprising the reactive product ofan A-side comprising a prepolymer diisocyanate and a B-side comprising afirst vegetable oil, a cross-linking agent comprised of amulti-functional alcohol and a catalyst, wherein the first vegetable oiland the cross-linking agent are substantially non-esterfied prior to theA-side reacting with the B-side.
 2. A method of preparing a materialcomprising the steps of combining an A-side material comprising aprepolymer diisocyanate with a B-side comprising a first vegetable oil,a cross-linking agent comprised of a multi-functional alcohol and acatalyst, wherein the first vegetable oil and the cross-linking agentare substantially non-esterfied prior to combining the A-side with theB-side.
 3. A material comprising the reactive product of an A-sidecomprising a prepolymer isocyanate and a B-side comprising a firstvegetable oil, a cross-linking agent comprised of a multi-functionalalcohol and a catalyst, wherein the first vegetable oil and thecross-linking agent are substantially non-esterfied prior to the A-sidereacting with the B-side.
 4. A method of preparing a material comprisingthe steps of combining an A-side material comprising with a B-sidematerial, wherein said A-side comprises a prepolymer isocyanate and aB-side wherein the B-side comprises a first vegetable oil, across-linking agent comprised of a multi-functional alcohol, a catalyst,and a blowing agent, wherein the first vegetable oil and thecross-linking agent are substantially non-esterfied prior to combiningthe A-side with the B-side.